CN101139317A - Organic semiconductor materials containing carbazole units and their synthesis - Google Patents

Abstract

An organic semiconductor material containing a carbazole unit and its synthesis into an organic semiconductor material containing a carbazole unit and its preparation method, and applying this type of material to organic flat panel displays, organic photovoltaic cells, organic optical storage, and organic field effect transistors , chemical and biological sensing and organic laser and other organic electronics fields, this material is a compound material that introduces substituents at the 1 and 8 positions of the carbazole unit, and has a structure such as (A): This material has: (1) easy to synthesize And it can be modified flexibly; (2) it can effectively realize the photoelectric properties of the modulation material; and (3) it has the advantages of high thermal stability and glass transition temperature. It can be expected that this type of material will become a photoelectric functional material with commercial potential.

Description

Organic semiconductor materials containing carbazole units and their synthesis

technical field

The invention belongs to the technical field of photoelectric materials. It specifically relates to an organic semiconductor material containing a carbazole unit and a preparation method thereof, and relates to the application of these light-emitting materials in organic electroluminescence, organic field effect tubes, organic solar cells, organic light storage, organic nonlinear optics, chemical and biological transmission applications in sensing and organic lasers.

technical background

Since 1987, the Tang Research Group of Kodak Company in the United States [Tang, C.W.; Van Slyke, S.A.Appl.Phys.Lett. 1987, 51, 913.] and the University of Cambridge in 1990 [Burruges, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Bum, P.L.; Holmes, A.B.Nature 1990, 347, 539.] published thin-film organic electroluminescent devices (Organic Light -emitting Diodes) and polymer light-emitting diodes (PolymericLight-emitting Diodes), organic flat panel display has become another generation of market-oriented display products after liquid crystal display. At the same time, other organic electronics and optoelectronic industries, including fields such as organic field effect transistors, organic solar cells, nonlinear optics, biosensing and lasers, and nonlinear optical materials are also moving toward marketization. The advantages of organic and plastic electronics lie in the low cost of material preparation, simple process, and the flexibility and plasticity of general-purpose polymers. Therefore, the development of new organic optoelectronic information materials with practical market potential has attracted the attention and investment of many scientists from different disciplines in universities at home and abroad, as well as research institutions and companies. So far, the development of new and highly stable carrier transport materials and light-emitting materials has become a key factor to improve the efficiency and lifetime of organic electronics, electro-optic and optoelectronic devices.

So far, due to the good optical and electrical properties of the carbazole structural unit, the ability of the carbazole structure to modulate electrons has been extensively studied in the literature and exhibits good modification characteristics. Carbazole-containing and derivative units are mainly used in the construction of hole transport materials, red light materials, multifunctional light-emitting materials, OTFT materials and organic solar cell materials, so their small molecular oligomers may become promising optoelectronic materials. However, there are still no literature and patent reports on photoelectric functional materials modified with 1,8-carbazole as the core, which greatly limits the application range of carbazole materials in organic photoelectric materials. Therefore, the present invention develops a series of novel 1,8-carbazoles as oligomers with high stability as the core, which are applied to organic electronics, optoelectronics, photonics or optoelectronic materials.

Contents of the invention

Technical problem: The purpose of this invention is to design and synthesize 1- and 8-substituted carbazole materials and their derivative materials, and point out organic electroluminescence, organic optical storage, organic field effect tubes and organic lasers of such materials. Applications in the field of electronics.

Technical solution: an organic semiconductor material containing carbazole units, which has the following structure:

Compound material 1

Wherein, the symbols and labels in the formula have the following meanings:

R ₁ , R ₂ , R ₃ are hydrogen or linear, branched or cyclic alkyl chains with 1 to 22 carbon atoms; or alkenyl, alkynyl, aryl with 2 to 40 carbon atoms, One or more carbon atoms can be replaced by heteroatoms Si, Se, O, S, N, S(O) ₂ , and the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano;

R ₄ , R ₅ , R ₆ , and R ₇ are the same or different when they appear, and are hydrogen or straight, branched or cyclic alkyl chains with 1 to 22 carbon atoms, one or more of which are not adjacent Carbon atom can be NR ₁₉ , O, S, -CO-O-, -O-CO-O-, -CO-NR ₁₉ -, -NR ₁₉ -CO-NR ₁₉ -, -O-CO-S-, -NR ₁₉ -CO-O-, -CS-O-, -CS-NR ₁₉ -, -O-CS-O-, -NR ₁₉ -CS-NR ₂₀ -, -O-CS-S-, -NR ₁₉ -CS-O-, -CS-S-, -SiR ₁₉ R ₂₀ -replacement, or one or more hydrogen atoms are replaced by fluorine or cyano;

R ₁₉ and R ₂₀ are the same or different when they appear, and are hydrogen or linear, branched or cyclic alkyl chains and alkoxy chains with 1 to 22 carbon atoms;

Ar ₁ and Ar ₂ appear the same or different, and are groups that can form a single chemical bond, including hydrogen, halogen, cyano, and conjugated groups; wherein the structural unit of the conjugated group has 2 to 40 carbon atoms Alkenyl, alkynyl, aryl, wherein one or more carbon atoms can be replaced by heteroatoms Si, Se, O, S, N, S(O) ₂ , and the hydrogen on one or more carbon atoms can be replaced by Fluorine or cyano substitution; specifically one of the following structures:

Among them, the symbols in the formula have the following meanings:

- ^* is the position area where Ar ₁ , Ar ₂ and carbazole are connected between the structural units; more than one - ^* means that one of them can be arbitrarily selected - ^* as the connection between them;

D ₁ , D ₂ , and D ₃ appear the same or different, and are CR ₁₉ R ₂₀ , NR ₁₉ , -O-, -S-, -Se-, -S(O) ₂ -or -SiR ₁₉ R ₂₀ - ;

E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ appear the same or different, and are CR ₁₉ , N, SiR ₁₉ ;

e, f, g appear the same or different, and are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

AC ₁ , AC ₂ , AC ₃ , and AC ₄ appear the same or different, and are phenyl, indenyl, naphthyl, azulenyl, fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, rylene, thienyl , pyrrolyl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indolyl, benzofuryl, benzothienyl, benzimidazolyl, quinolinyl, isoquinolyl, quinoxaline Base, carbazolyl, o-phenanthrenyl; or its structure of alkyl, fluorine substitution, oxidation derivatives.

In compound material I, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are preferably selected from hydrogen or n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl or n-octyloxy chain; in addition, R ₁ is also preferably phenyl, 4-tert-butylphenyl.

In the compound material I, Ar ₁ and Ar ₂ appear the same or different, and are preferably one of the following structures;

In Compound Material I, Molecular Material I takes precedence over the following structures:

In the synthesis method of the compound material I, the key intermediates of 1,8-dibromocarbazole and its derivatives are prepared first, and then the compound material I is prepared through a coupling reaction. The preparation of 1,8-dibromocarbazole and its derivatives takes N-ethyl-3,6-di-tert-butyl-1,8-dibromocarbazole as an example, and the specific synthetic route is as follows:

Among them, step ① includes alkylation reaction under the condition of KOH/DMSO/bromoethane; step ② is tert-butylation under the condition of tBuCl/ZnCl ₂ /CH ₂ NO ₃ ; step ③ is in AcOH/ Bromination reaction is carried out under the condition of Br ₂ ; step ④ carries out borylation reaction under the action of n-Buli/organic borate.

In the synthetic method of preparing compound material I, mainly comprise carbon-carbon bond or carbon-heteroatom coupling reaction method, comprise Gilch (is the arylmethyl halide alkenylation coupling reaction under potassium tert-butoxide catalysis), Witting (is the alkenylation coupling reaction of aldehydes and organophosphine derivatives), Ullmann (is the C-N bond formation reaction catalyzed by copper), Stille (is the C-C coupling reaction of tin reagents catalyzed by palladium), Suzuki (is the palladium catalyzed C-C coupling reactions of boron reagents), Yamamoto (C-C coupling reactions between aryl halides under nickel catalysis), Heck (palladium-catalyzed arylation and alkenylation coupling reactions of alkenes) or Rieke (palladium-catalyzed C-C coupling reactions of zinc reagents under catalysis) transition metal palladium catalyzed methods; also include other linking reactions by means of heterocyclic ring formation.

Among them, method (1) Suzuki coupling reaction: the reactants are aryl diboronic acid and/or aryl dihalide and 2 equivalents of aryl monohalide and/or aryl monoboronic acid, or mixed aromatic halide/boronic acid , realize coupling with palladium catalyst; The consumption of catalyst is 0.1 to 20mol%; Suitable solvent is weak polar or polar aprotic organic solvent or its mixed solvent; Reaction temperature is 30 to 150 ℃; Reaction time is 1 to 7 days;

Method (2) is a Stille coupling reaction: here reactant is dihalide and/or disstannate and monostannate and/or monohalide, or corresponding monohalide-monostannate derivative mono Body, under basic conditions and in the presence of palladium catalyst and solvent coupling;

Method (3) is a Yamamoto coupling reaction: the reactant is a halide; under alkaline conditions, Ni(0) or Ni(II) or compound catalysis and solvent conditions, the reaction is carried out; the reaction conditions are Ni(COD) ₂ / bpy/1,5-cyclooctadiene/DMF (COD=1,5-cyclooctadiene).

Beneficial effects: characterized by elemental analysis, infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), chromatography-mass on-line (GCMS), matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS), and gel chromatography (GPC) The structure of polymer and polymer materials was studied, the thermal stability of the materials was tested by thermogravimetric analysis and differential thermal analysis, and their electrochemical properties were characterized by cyclic voltammetry.

Among them, the thermogravimetric analysis and differential thermal analysis tests of this kind of materials show good thermal stability; the electrochemical properties of carbazole blue light materials characterized by cyclic voltammetry show that the oxidation potential is greatly reduced, and the space efficiency is effectively improved. Hole injection capability; and the blue light material maintains high luminous efficiency. Therefore, devices composed of this type of material can be represented as efficient and stable organic electroluminescent devices.

This type of molecular material can also be applied to organic electronic fields such as organic semiconductor layers in field effect transistors, solar photovoltaic cells, organic laser materials, and organic nonlinear optical materials. Compound material I is suitable for plastic electronic materials and optoelectronic materials; devices or components in the field of plastic electronics include polymers and organic light-emitting diode devices, organic solar cells, organic laser diode devices, organic optical storage, organic field effect transistors, organic thin film transistors, Organic integrated circuits, biosensor devices, nonlinear optical elements, etc.; used as organic electronic materials include light-emitting materials, electron and hole transport materials, interface injection materials, conductive materials, photoelectric materials, conductive materials, superconducting materials, color-changing materials Material.

In addition, on this basis, preliminary devices were designed to evaluate various light emission behaviors of carbazole materials. Devices are designed and studied for carrier injection and transport performance, material luminescence performance, host-guest energy transfer behavior and light amplification behavior when used as white light and phosphorescent host materials. The transparent anode is made on a glass or plastic substrate, and then the hole transport material is vacuum evaporated on the conductive layer, and the compound in the present invention is evaporated or spin-coated as a light-emitting layer or a doped host material, and then a layer of electrons is evaporated. The transport layer, and finally the cathode is evaporated. The experimental results show that these carbazole-containing materials can be used as carrier injection and transport materials, luminescent materials, and white light and phosphorescent host materials with excellent comprehensive performance.

The main advantages of the present invention are:

1. The route of synthesis is flexible, and there is a large space for modification.

2. Red light materials and other push-pull electron systems can be effectively constructed by introducing electron-deficient groups.

3. It maintains a high glass transition temperature and high thermal stability, and has good evaporation performance.

Description of drawings:

Figure 1. Molecular weight characterization of 3,6-di-tert-butyl-9-ethyl-1,8-bis(pyren-1-yl)-carbazole.

Figure 2. Thermal analysis characterization of 3,6-di-tert-butyl-9-ethyl-1,8-bis(pyren-1-yl)-carbazole. Wherein Fig. 2 (a) represents the ultraviolet absorption spectrum; Fig. 2 (b) represents the fluorescence emission spectrum.

Figure 3.3, Absorption emission spectrum characterization of 6-di-tert-butyl-9-ethyl-1,8-bis(pyren-1-yl)-carbazole. Wherein Fig. 3 (a) represents thermogravimetric analysis result; Fig. 3 (b) represents DSC differential calorimetry scanning analysis result.

Detailed ways

In order to better understand the content of the patent of the present invention, the technical solution of the present invention will be further illustrated through specific examples below, including synthesis, property determination and device preparation. However, these implementation examples do not limit the present invention.

Embodiment 1, compound material containing carbazole and pyrene:

9-Ethyl-carbazole

9-ethyl-9H-carbazole

Mix 5g carbazole, 3g KOH, and 30ml DMSO in a three-necked flask, add 4ml bromoethane dropwise at 85 degrees, stir and react for 3 hours, add 100ml water after cooling and mix, and leave to stand for a light yellow solid to precipitate, filter, After drying and recrystallization from absolute ethanol, the product was obtained as white needle crystals (yield 90%).

GC-MS (EI-m/z): 195 (M ⁺ ).

3,6-di-tert-butyl-9-ethyl-carbazole

3,6-di-tert-butyl-9-ethyl-9H-carbazole

Take 9-ethyl-carbazole (20mmol), 100mlCH ₂ NO ₃ , and zinc chloride (8.1g, 60mmol) are mixed in a three-necked flask, and under nitrogen, tert-butyl chloride (6.5ml, 60mmol ) was added dropwise in the reaction flask, and after 5 hours of normal temperature reaction, 200ml of water was added to quench the reaction, extracted with dichloromethane, dried, and rotary evaporated to obtain a white product (94% yield).

GC-MS (EI-m/z): 307 (M ⁺ ).

3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole

3,6-di-tert-butyl-1,8-dibromo-9-ethyl-9H-carbazole

Take 3,6-di-tert-butyl-9-ethyl-carbazole (54mmol) and dissolve it in 1.5L glacial acetic acid, and add liquid bromine (6.2ml, 120mmol) dropwise to the reaction flask under light-shielded conditions , after 1 hour of reaction, water and sodium thiosulfate were added to quench the reaction and neutralize excess bromine. Extracted with dichloromethane, dried, and rotary evaporated to obtain the product (98% yield).

GC-MS (EI-m/z): 465 (M ⁺ ).

1-Bromopyrene

1-bromopyrene

Take pyrene (12.5mmol) and dissolve it in DMF (17.42ml), and dissolve NBS (2.046g, 11.5mmol) in DMF (21.78ml), add dropwise under ice water and mix the reaction. Diluted with water, extracted with ether, dried and rotary evaporated, and purified with petroleum ether silica gel column to obtain a white solid (yield 84.6%).

GC-MS (EI-m/z): 280 (M ⁺ ).

Pyrene boronic acid

pyren-1-yl-1-boronic acid

First, take bromopyrene (2.53 mmol) and put it into a 250 mL two-necked flask. The flask has been heat-dried and airtight, and then evacuated and vented with nitrogen three times. Then, the reaction apparatus was put into a low temperature bath of -78°C generated by dry ice and acetone, and freshly distilled tetrahydrofuran (20 mL) was taken anhydrous and oxygen free. Subsequently, n-butyllithium (2.373mL, 3.800mmol, 1.6Msolution in hexane) was slowly added to the two-necked flask, and reacted at a low temperature of -78°C for about 1 hour, and finally, 2-isopropyl borate (5.064mmol) was quickly injected into the reactor, and the reaction was slowly returned to room temperature, and the reaction was overnight. After the reaction was completed, it was hydrolyzed with three times the amount of dilute hydrochloric acid for 3 hours, the reaction was quenched with ice water, washed with sodium chloride and extracted with ether, dried, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by recrystallization in n-hexane/dichloromethane mixed solvent to obtain a white solid (80%).

3,6-di-tert-butyl-9-ethyl-1,8-bis(pyrene-1-yl)-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-di(pyren-1-yl)-9H-carbazole

Take pyreneboronic acid (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (1.0equiv., 1.35mmol) and dissolve them in 20mL of toluene and Add the catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg) to the mixed solvent of tetrahydrofuran, avoid light and pass nitrogen, then add K ₂ CO ₃ (2.71mL, 2mol/L, 4equiv.), at 90°C The reaction was carried out under low temperature for 48 hours. After the reaction, water was added, extracted with CHCl ₃ , dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (3:1) to obtain a white solid (91% yield).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 707.

Embodiment 2, compound material containing carbazole and anthracene:

10-bromoanthracene

10-bromoanthracene

Anthracene (12.5mmol) was dissolved in DMF (17.42mL), and NBS (2.046g, 11.5mmol) was dissolved in DMF (21.78mL), and mixed reaction was added dropwise under ice water. Diluted with water, extracted with ether, dried and rotary evaporated, and purified with petroleum ether silica gel column to obtain a white solid (yield 88%).

GC-MS (EI-m/z): 280 (M ⁺ ).

10-Anthraceneboronic acid

anthracen-10-yl-10-boronic acid

First, take 10-bromoanthracene (2.53mmol) and put it into a 250mL two-necked flask. The flask has been heat-dried and airtight, and then evacuated three times with nitrogen. Then, the reaction apparatus was put into a low temperature bath of -78°C generated by dry ice and acetone, and freshly distilled tetrahydrofuran (20 mL) was taken anhydrous and oxygen free. Subsequently, n-butyllithium (2.373mL, 3.800mmol, 1.6M solution in hexane) was slowly added to the two-necked flask, and reacted at a low temperature of -78°C for about 1 hour. Finally, 2-isopropylboronic acid The ester (5.064 mmol) was quickly injected into the reactor, and the reaction was slowly returned to room temperature, and the reaction was carried out overnight. After the reaction was completed, it was hydrolyzed with three times the amount of dilute hydrochloric acid for 3 hours, the reaction was quenched with ice water, washed with sodium chloride and extracted with ether, dried, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by recrystallization in n-hexane/dichloromethane mixed solvent to obtain a white solid (yield 78%).

3,6-di-tert-butyl-9-ethyl-1,8-di(anthracene-10-yl)-carbazole

3,6-di-tert-butyl-1,8-di(anthracen-10-yl)-9-ethyl-9H-carbazole

Take anthracenboronic acid (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (1.0equiv., 1.35mmol) and dissolve them in 20mL of toluene and Add the catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg) to the mixed solvent of tetrahydrofuran, avoid light and pass nitrogen, then add K ₂ CO ₃ (2.71mL, 2mol/L, 4equiv.), at 90°C The reaction was carried out for 48 hours. After the reaction, water was added, extracted with CHCl ₃ , dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (3:1) to obtain a white solid (92% yield).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 659.

Embodiment 3, compound material containing carbazole and benzanthracene:

10-Bromo-9-phenylanthracene

10-bromo-9-phenylanthracene

Dissolve 9-phenylanthracene (1.5g, 5.9mmol) in acetic acid (80mL), heat to 65°C under nitrogen atmosphere, and add bromine (1.04g, 6.5mmol) dissolved in acetic acid (20mL) dropwise into the reaction flask. After the dropwise addition, the reaction was allowed to return to room temperature, crystals were precipitated, and filtered to obtain a yellow solid (92% yield).

GC-MS (EI-m/z): 280 (M ⁺ ), mp 154°C.

9-Phenylanthracene-10-yl-10-boronic acid

9-phenylanthracen-10-yl-10-boronic acid

First, take 10-bromo-9-phenylanthracene (2.53mmol) and put it into a 250ml two-necked flask. The flask has been heated, dried and airtight, and then vacuumed three times with nitrogen. Oxygen device for processing use. Then, the reaction apparatus was put into a low temperature bath of -78°C generated by dry ice and acetone, and freshly distilled tetrahydrofuran (20 mL) was taken anhydrous and oxygen free. Subsequently, n-butyllithium (2.373mL, 3.800mmol, 1.6M solution in hexane) was slowly added to the two-necked flask, and reacted at a low temperature of -78°C for about 1 hour. Finally, 2-isopropylboronic acid The ester (5.064 mmol) was quickly injected into the reactor, and the reaction was slowly returned to room temperature, and the reaction was carried out overnight. After the reaction was completed, it was hydrolyzed with three times the amount of dilute hydrochloric acid for 3 hours, the reaction was quenched with ice water, washed with sodium chloride and extracted with ether, dried, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by recrystallization in n-hexane/dichloromethane mixed solvent to obtain a white solid (76%).

3,6-di-tert-butyl-9-ethyl-1,8-bis(10-phenylanthracene-9-yl)-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-bis(10-phenylanthracen-9-yl)-9H-carbazole

Take 9-phenylanthracene-10-yl-10-boronic acid (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (1.0equiv ., 1.35mmol) were mixed and dissolved in a mixed solvent of 20mL toluene and tetrahydrofuran, the catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg) was added, and nitrogen was ventilated in the dark, and then K ₂ CO ₃ (2.71mL, 2mol/ L, 4equiv.), reacted at 90°C for 48 hours, added water after the reaction, extracted with _CHCl3 , dried and rotary evaporated, petroleum ether: dichloromethane mixed solvent (3: 1) silica gel column purification, to obtain a white solid (92% yield).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 811.

Embodiment 4, compound material containing carbazole and triphenylamine:

1-(Diphenylamino)4-bromobenzene

1-(diphenylamino)-4-bromobenzene

1.23g (0.005mol) triphenylamine was added in a 100mL round bottom flask, dissolved with 12.5mL DMF and shaken to obtain a colorless clear solution, and 99% N-bromosuccinimide (NBS) was dissolved in 12.5 In 0.5 mL of DMF, shake well, the solution turns light yellow, add it dropwise to the triphenylamine solution within 0.5 hours, and stir vigorously while adding. The whole reaction was reacted at room temperature for 24 hours under the condition of shielding from light. The reaction solution turned from light yellow to clear. After the reaction was completed, DMF was removed by distillation under reduced pressure, and purified by silica gel chromatography (eluent: V _{ethyl acetate} : V _{petroleum ether} = 1:50). The eluate of the product was spun to dryness to obtain a white solid (93% yield).

4-(Diphenylamino)phenylboronic acid

4-(diphenylamino)phenylboronic acid

First, take 1-(diphenylamino)-4-bromobenzene (2.53mmol) and put it into a 250mL two-necked flask. The flask has been heated, dried and airtight, and then evacuated and vented with nitrogen three times. Use in anhydrous and anaerobic equipment. Then, the reaction apparatus was put into a low temperature bath of -78°C generated by dry ice and acetone, and freshly distilled tetrahydrofuran (20 mL) was taken anhydrous and oxygen free. Subsequently, n-butyllithium (2.373mL, 3.800mmol, 1.6M solution in hexane) was slowly added to the two-necked flask, and reacted at a low temperature of -78°C for about 1 hour. Finally, 2-isopropylboronic acid The ester (5.064 mmol) was quickly injected into the reactor, and the reaction was slowly returned to room temperature, and the reaction was carried out overnight. After the reaction was completed, it was hydrolyzed with three times the amount of dilute hydrochloric acid for 3 hours, the reaction was quenched with ice water, washed with sodium chloride and extracted with ether, dried, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by recrystallization in n-hexane/dichloromethane mixed solvent to obtain a white solid (yield 77%).

3,6-di-tert-butyl-9-ethyl-1,8-bis(4-(diphenylamino)phen-1-yl)-carbazole

3,6-di-tert-butyl-1,8-bis(4-(diphenylamino)benzene-1-yl)-9-ethyl-9H-carbazole

Take 4-(diphenylamino)phenylboronic acid (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (1.0equiv., 1.35mmol ) were mixed and dissolved in a mixed solvent of 20mL toluene and tetrahydrofuran, the catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg) was added, and nitrogen was vented in the dark, and then K ₂ CO ₃ (2.71mL, 2mol/L, 4equiv. ), reacted under the condition of 90 ℃ for 48 hours, added water after the reaction, used CHCl ₃ extraction, dried and rotary evaporated, sherwood oil: dichloromethane mixed solvent (3: 1) silica gel column purification, obtained white solid (yield is 86%).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 793.

Embodiment 5, compound material containing carbazole and phenanthroline:

3,6-di-tert-butyl-1,8-di(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)-9-ethyl -carbazole

3,6-di-tert-butyl-1,8-bis[4,4,5,5-tetramethyl-1,3,2-Dioxaborolane-yl]-9-ethyl-9H-carbazole

First, put 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (1.0 equiv.) into a 250mL two-necked flask, which has been heat-dried and sealed The last three vacuum pumping nitrogen, high-purity nitrogen before use through strict anhydrous oxygen-free device treatment. Then, the reaction apparatus was put into a low temperature bath of -78°C generated by dry ice and acetone, and freshly distilled tetrahydrofuran (20 mL) was taken anhydrous and oxygen free. Then n-butyllithium (3.0equiv.) was slowly added to the two-necked flask, and reacted at a low temperature of -78°C for about 1 hour, and finally, 2-isopropoxy-4,4,5,5- Tetramethyl-1,3,2-dioxaborane (3.0 equiv.) was quickly injected into the reactor, and the reaction was slowly returned to room temperature, and the reaction was carried out overnight. After the reaction was completed, the reaction was quenched with ice water, washed with sodium chloride and extracted with ether, dried, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by recrystallization in n-hexane/toluene mixed solvent to obtain white solid (yield 82%).

3-bromo-1,10-phenanthroline

3-bromo-1, 10-phenanthroline

After getting phenanthroline (2.93g, 14.8mmol) and KBr (2.11g, 17.8mmol), then, mixed concentrated nitric acid and concentrated sulfuric acid (being respectively 18mL and 36mL) were put into the reaction flask, and the reactor was quickly Heating to 100°C and maintaining reflux for 12 hours, after the reaction, pour the reaction solution into ice water, and neutralize the solution to pH 7 with NaOH solid. After filtering, the soluble solid was washed into the filtrate with CHCl ₃ and extracted with CHCl ₃ . The filtrate was dried, rotary evaporated, and recrystallized from water to obtain a light yellow solid product (yield 70%).

GC-MS (EI-m/z): 258 (M ⁺ ).

3,6-di-tert-butyl-9-ethyl-1,8-bis(1,10-phenanthroline-3-yl)-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-bis(1,10-phenanthroline-3-yl)-9H-carbazole

Take 3-bromo-1,10-phenanthroline (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-bis(4,4,5,5-tetramethyl-[ 1,3,2] Dioxaborolyl)-9-ethyl-carbazole (1.0equiv., 1.35mmol) was mixed and dissolved in 20mL of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh ₃ ) was added ₄ (5mol%, 156.6mg), protected from light and nitrogen, then added K ₂ CO ₃ (2.71mL, 2mol/l, 4equiv.), reacted at 90°C for 48 hours, added water after the reaction, and used CHCl ₃ Extraction, drying and rotary evaporation, petroleum ether: dichloromethane mixed solvent (1:3) silica gel column purification to obtain a white solid (yield 83%).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 663.

Embodiment 6, compound material containing carbazole and benzo[1,2,5]thiadiazole:

4-(4-tert-butylphenyl)-7-bromobenzo[1,2,5]thiadiazole

4-(4-tert-butylphenyl)-7-bromobenzo[c][1,2,5]thiadiazole

4,7-Dibromobenzo[1,2,5]thiadiazole (1.00g, 3.40mmol) was dissolved in benzene (32mL), and aqueous sodium carbonate solution (21mL, 2M) and 4-tert-butyl Phenylphenylboronic acid (3.40mmol) was dissolved in ethanol (20mL), and the reaction was maintained under a nitrogen atmosphere, and then Pd(PPh ₃ ) ₄ (0) (118mg, 0.102mmol) was added to the reaction solution at 60°C, and after mixing Reaction at 80°C for 15h. After the reaction, the mixed solution was poured into water and extracted with chloroform, the organic phase was dried, rotary evaporated, and the silica gel column (eluent: dichloromethane/n-hexane, 1:1 (v/v)) was separated to give the product (the yield was 75%).

GC-MS (EI-m/z): 346 (M ⁺ ).

3,6-di-tert-butyl-9-ethyl-1,8-bis(4-(4-tert-butylphenyl)benzo[1,2,5]thiadiazol-7-yl )-carbazole

3,6-di-tert-butyl-1,8-bis(4-(4-tert-butylphenyl)benzo[c][1,2,5]thiadiazol-7-yl)-9-ethyl-9H-carbazole

Take 4-(4-tert-butylphenyl)-7-bromobenzo[1,2,5]thiadiazole (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1, 8-bis(4,4,5,5-tetramethyl-[1,3,2]dioxaborolyl)-9-ethyl-carbazole (1.0equiv., 1.35mmol) mixed and dissolved In the mixed solvent of 20mL toluene and tetrahydrofuran, add catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg), avoid light and ventilate nitrogen, then add K ₂ CO ₃ (2.71mL, 2mol/l, 4equiv.), in Reacted at 90°C for 48 hours, added water after the reaction, extracted with _CHCl3 , dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether: dichloromethane (1:3) to obtain a white solid (83% yield) .

MALDI-TOF-MS (m/z)/[M ⁺ ]: 839.

Embodiment 7, compound material containing carbazole and oxadiazole:

4-Bromophenylhydrazide

4-bromobenzohydrazide

Methyl 4-bromobenzoate (27.0 g, 126 mmol) and NH ₂ NH ₂ ·H ₂ O (34.1 g, 502 mmol) were mixed in 200 mL of ethanol and refluxed for 24 hours. After the reaction, it was cooled to room temperature and poured into cold water to form a white solid, which was filtered, washed with petroleum ether to remove the reactant, and dried to obtain a white powder (yield 88%).

GC-MS (EI-m/z): 214 (M ⁺ ).

4-Bromo N'-(4-tert-butylbenzoyl)phenylhydrazide

4-bromo-N′-(4-tert-butylbenzoyl)benzohydrazide

4-Bromophenylhydrazide (10.0g, 46.5mmol) and Na ₂ CO ₃ (9.9g, 93.5mmol) were dissolved in NMP (80mL), and then 4-tert-butylbenzoyl chloride (9.1g, 46.5mmol) It was also dissolved in NMP (20 mL), and slowly added dropwise to 4-bromophenylhydrazide, and reacted at room temperature for 24 hours. After the reaction was completed, it was poured into cold water to form a white solid, which was filtered, washed, and dried to obtain a white powder product (100% yield).

GC-MS (EI-m/z): 374 (M ⁺ ).

2-(4-bromobenzene)-5-(4-tert-butylbenzene)-1,3,4-oxadiazole

2-(4-bromophenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole

In a 250 mL three-neck flask, 4-bromo N'-(4-tert-butylbenzoyl)phenylhydrazide (5.0 g, 13.4 mmol) was dissolved in phosphine oxychloride (100 mL). Under nitrogen atmosphere, the mixture was refluxed for 6 hours. After the reaction, it was poured into cold water to form a white solid, which was filtered, washed, and dried to obtain a white powder product, which was finally recrystallized in acetone to obtain a white product (56% yield).

GC-MS (EI-m/z): 356 (M ⁺ ).

3,6-Di-tert-butyl-9-ethyl-1,8-bis(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazole-2- base) phenyl)-carbazole

3,6-di-tert-butyl-1,8-bis(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)phenyl)-9-ethyl-9H- carbazole

Take 2-(4-bromobenzene)-5-(4-tert-butylbenzene)-1,3,4-oxadiazole (2equiv., 2.71mmol) and 3,6-di-tert-butyl- 1,8-bis(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)-9-ethyl-carbazole (1.0equiv., 1.35mmol) Mix and dissolve in 20mL of a mixed solvent of toluene and tetrahydrofuran, add catalyst Pd(PPh ₃ ) ₄ (5mol%, 156.6mg), avoid light and pass nitrogen, then add K ₂ CO ₃ (2.71mL, 2mol/l, 4equiv.) , reacted at 90°C for 48 hours, added water after the reaction, extracted with CHCl ₃ , dried and rotary evaporated, petroleum ether: dichloromethane mixed solvent (1: 3) silica gel column purification, to obtain a white solid (yield: 83 %).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 859.

Embodiment 8, compound material containing carbazole and distyryl:

2-Bromo-1,1-stilbene

2-bromo-1, 1-diphenylethene

Dissolve 1,1-stilbene (3.4mL, 19.3mmol) in CCl ₄ (15mL), similarly dissolve liquid bromine (1mL, 19.5mmol) in CCl ₄ (15mL), then add it dropwise into 1,1-stilbene, and immediately HBr was produced, after the dropwise addition was completed, NaOH was added to neutralize, extracted, and passed through the column to obtain an oily liquid product (yield 85%).

GC-MS (EI-m/z): 258 (M ⁺ ).

3,6-di-tert-butyl-9-ethyl-1,8-bis(2,2-distyryl)-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-bis(2,2-diphenylvinyl)-9H-earbazole

Take 2-bromo-1,1-stilbene (2equiv., 2.71mmol) and 3,6-di-tert-butyl-1,8-bis(4,4,5,5-tetramethyl-[ 1,3,2] Dioxaborolyl)-9-ethyl-carbazole (1.0equiv., 1.35mmol) was mixed and dissolved in 20mL of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh ₃ ) was added ₄ (5mol%, 156.6mg), protected from light and nitrogen, then added K ₂ CO ₃ (2.71mL, 2mol/l, 4equiv.), reacted at 90°C for 48 hours, added water after the reaction, and used CHCl ₃ Extraction, drying and rotary evaporation, petroleum ether: dichloromethane mixed solvent (1:3) silica gel column purification to obtain a white solid (yield 88%).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 663.

Embodiment 9, compound material containing carbazole and dicyano vinyl:

3,6-di-tert-butyl-9-ethyl-1,8-dialdehyde-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-diformyl-9H-carbazole

Add n-BuLi (1.1 mL, 2.5M in hexane, 2.8 mmol) dropwise to 3,6-di-tert-butyl-1,8-dibromo-9 dissolved in THF (60 mL) at 0°C -Ethyl-carbazole (1.0equiv., 2.8mmol), stirred at room temperature for 1 hour, passed dry CO ₂ (the gas was dried with CaCl ₂ ) gas into the reaction flask for 15 minutes, and then the solvent was spun to dryness , and then dissolved it in THF (60 mL), and added nBuLi (7.5 mL, 1.5M in pentane, 11.3 mmol) dropwise into the reaction flask at a low temperature of -78°C, and returned to room temperature for 3 hours. Returning to the condition of -78°C, dry DMF (1.0 mL, 12.9 mmol) was added dropwise into the reaction bottle, and the reactant was allowed to return to normal temperature and reacted overnight. After the reaction was completed, it was hydrolyzed with HCl (1M, 10mL), then diluted with AcOEt (100ml), the organic phase was washed with NaOH (1M, 2×50mL) and Na ₂ CO ₃ (1M, 2×50mL), and dried. Filtration, rotary evaporation to obtain a crude product, and recrystallization with hot n-hexane to obtain a yellow product (yield 59%).

3,6-di-tert-butyl-9-ethyl-1,8-bis(2,2-dicyanovinyl)-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-bis(2,2-dicyanovinyl)-9H-carbazole

Dissolve 3,6-di-tert-butyl-9-ethyl-1,8-dialyl-carbazole (0.6 mmol) and propanedicyanide (8.72 mg, 1.23 mmol) in DMSO (6 mL) Reacted at 110°C for 5 hours, the reaction turned from initial yellow to dark red. On cooling, the precipitate was filtered and washed with MeCN to give the product (97% yield).

Embodiment 10, compound material containing carbazole and boron:

3,6-di-tert-butyl-9-ethyl-1,8-bis(4-bis(2,4,6-trimethylphenyl)boryl)-carbazole 3,6-di- tert-butyl-9-ethyl-1, 8-bis(dimesitylboryl)-9H-carbazole

Add the aforementioned 3,6-di-tert-butyl-1,8-dibromo-9-ethyl-carbazole (0.0029mol) into a 150ml three-necked flask, and add 50mL of freshly distilled THF to dissolve it. Use a dry ice-acetone cooling bath to lower the temperature to -78°C, extract 4mL (2.5mol/l) of n-butyllithium n-hexane solution with a syringe, pour it into a three-necked bottle, stir for 30min, remove the cooling bath, and let the temperature rise naturally for 2h. The temperature was lowered to -78°C. Under nitrogen protection, dimethyl boron fluoride (2 g, 0.007 mol) was dissolved in about 6 mL THF, and quickly injected into the three-necked bottle with a syringe. Naturally rise to room temperature under stirring for 24 hours, and then pour the reaction solution into 100 mL of distilled water. _Extracted three times with chloroform, dried without _Na2SO4 for 24h, and evaporated the solvent on a rotary evaporator. Then separated and purified by column chromatography, and the eluent was chloroform:petroleum ether=1:6(V:V). One layer of blue-green fluorescence, the solution was evaporated to dryness with a rotary evaporator to obtain a bright yellow powder (yield 4%).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 804.

Embodiment 11, the compound material containing carbazole and (dicyano methylene)-pyran:

3,6-Di-tert-butyl-9-ethyl-1,8-bis((1E)-2-(6-tert-butyl 4-(dicyanomethylene)-4H-pyran -2-yl)vinyl)-carbazole

3,6-di-tert-butyl-1,8-bis((1E)-2-(6-tert-butyl-4-(dicyanomethylene)-4H-pyran-2-yl)vinyl)-9-ethyl- 9H-carbazole

3,6-di-tert-butyl-9-ethyl-1,8-dialdehyde-carbazole (2.88mmol), 2-(2-tert-butyl-6-methyl-4H-pyran -4-methylene)propanedicyanide (1.846g, 8.62mmol), and pyridine (732mg, 8.62mmol) were dissolved in ethanol (46mL) and refluxed for 2 days. Ethanol was distilled off under reduced pressure, and the crude product was re-dissolved in dichloromethane (20 mL), washed with water, extracted with dichloromethane (20 mL×2), dried, rotary evaporated, purified with a silica gel column (eluent: CHCl ₃ ), and finally Recrystallized from ethyl acetate (68% yield).

MALDI-TOF-MS (m/z)/[M ⁺ ]: 755.

Embodiment 12, to the photoluminescence spectrum and quantum efficiency measurement of carbazole-containing material:

The product was made into a precise 1 μM dilute solution in chloroform and flushed with argon to remove oxygen. The absorption and emission spectra were measured by Shimadzu UV-3150 ultraviolet-visible spectrometer and RF-530XPC fluorescence spectrometer. The photoluminescence spectrum is measured at the wavelength of maximum absorption of ultraviolet absorption. The photoluminescence spectrum of the solid film was carried out through a vacuum-evaporated quartz plate with a film thickness of 300 nm. The fluorescence quantum efficiency of the solution of the blue light material was measured by a solution of 1 μM 9,10-diphenylanthracene in cyclohexanone as a standard.

Embodiment 13, to the thermal analysis determination of carbazole-containing material:

Thermogravimetric analysis (TGA)) was performed on a Shimadzu DTG-60H thermogravimetric analyzer with a heating scan rate of 10°C/min and a nitrogen flow rate of 20 cm ³ /min. Differential scanning calorimetry (DSC) was carried out on a Shimadzu DSC-60A tester. The sample was first heated at a rate of 10°C/min to a state ten degrees lower than the decomposition temperature of the sample, and then, under liquid nitrogen conditions The temperature was lowered back to the starting temperature, and the temperature was scanned at a rate of 10°C/min for the second time.

Embodiment 14, to the electrochemical determination of carbazole-containing material:

Electrochemical cyclic voltammetry (CV) experiments were performed on an Eco Chemie BVAUTOLAB potentiostat voltammetry analyzer using a three-electrode system, including a platinum-carbon working electrode, Ag/Ag ⁺ as a reference electrode, and a platinum wire as a counter electrode. Dichloromethane was used as a solvent in the oxidation process, tetrahydrofuran was used as a solvent in the reduction process, tetrabutylammonium hexafluorophosphine (Bu ₄ N ⁺ PF ₆ ^- ) was used as a supporting electrolyte, and the concentration was 0.1M. All electrochemical experiments were carried out under nitrogen atmosphere at room temperature, and the voltage scanning speed was 0.1V/s. Using ferrocene (FOC) as a benchmark, the HOMO and LUMO energy levels of the material can be calculated by measuring the onset voltages of the oxidation and reduction processes.

Example 15, preparation of electroluminescent devices containing carbazole materials:

A preparation of a carbazole-containing material as a light-emitting layer device: ITO/light-emitting layer/BCP or TPBI (370 Ȧ)/LiF (5 Ȧ)/Al, wherein ITO is a transparent electrode with a sheet resistance of 10-20Ω/□; The carbazole-containing material is used as the light-emitting layer by vacuum thermal evaporation technology, the evaporation speed is 1-2 Ås, and the film thickness is 10-200nm; then BCP or TPBI and LiF buffer layer are evaporated; finally, the aluminum cathode is evaporated.

Claims (7)

1. An organic semiconductor material containing carbazole units is characterized in that the material is a compound material with substituent groups introduced at 1 and 8 positions of carbazole units, and has the following structure:

compound material I

In the formula: r₁、R₂、R₃Is hydrogen or has 1 to 22 carbon atomsA linear, branched or cyclic alkyl chain; or alkenyl, alkynyl, aryl having 2 to 40 carbon atoms, where one or more carbon atoms may be interrupted by heteroatoms Si, Se, O, S, N, S (O)₂Substituted, hydrogen on one or more carbon atoms may be substituted by fluorine or cyano;

R₂、R₅、R₆、R₇identical or different in the occurrence and is hydrogen or a straight, branched or cyclic alkyl chain having from 1 to 22 carbon atoms, where one or more nonadjacent carbon atoms may be replaced by N-R₁₉、O、S、-CO-O-、-O-CO-O-、-CO-NR₁₉-、-NR₁₉-CO-NR₁₉-、-O-CO-S-、-NR₁₉-CO-O-、-CS-O-、-CS-NR₁₉-、-O-CS-O-、-NR₁₉-CS-NR₂₀-、-O-CS-S-、-NR₁₉-CS-O-、-CS-S-、-SiR₁₉R₂₀-by replacement, or wherein one or more hydrogen atoms are replaced by fluorine or cyano;

R₁₉、R₂₀identical or different in the occurrence and is hydrogen or a linear, branched or cyclic alkyl chain having from 1 to 22 carbon atoms and an alkoxy chain;

Ar₁、Ar₂identical or different in occurrence and are groups which may form a single chemical bond, including hydrogen, halogen, cyano, and conjugated groups; wherein the conjugated radical structural unit is alkenyl, alkynyl or aryl having 2 to 40 carbon atoms, one or more of which may be interrupted by heteroatoms Si, Se, O, S, N, S (O)₂Substituted, hydrogen on one or more carbon atoms may be substituted by fluorine or cyano; the structure is specifically one of the following structures:

wherein the symbols in the formula have the following meanings:

-^*is Ar between structural units₁、Ar₂A positional region linked to carbazole; greater than one^*One of which can be arbitrarily selected^*As a result of whichThe connection between them;

D₁、D₂、D₃identical or different in the occurrence and is CR₁₉R₂₀、NR₁₉、-O-、 -S-、-Se-、-S(O)₂-or-SiR₁₉R₂₀-；

E₁、E₂、E₃、E₄、E₅、E₆Identical or different in the occurrence and is CR₁₉、N、SiR₁₉；

e. f, g are the same or different at occurrence and are independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;

AC₁、AC₂、AC₃、AC₄identical or different when appearing, and is any one of phenyl, indenyl, naphthyl, azulenyl, fluorenyl, phenanthryl, anthracyl, pyrenyl, rylenphenyl, thienyl, pyrrolyl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indolyl, benzofuryl, benzothienyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl and o-diazaphenanthryl; or an alkyl, fluoro-substituted, oxidized derivative of its structure.

2. The carbazole unit-containing organic semiconductor material according to claim 1, wherein R in the compound material I is₁、R₂、R₃、R₄、R₅、R₆、R₇Respectively selected from any one of hydrogen or n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl or n-octyloxy chains.

3. The carbazole unit-containing organic semiconductor material according to claim 1, wherein Ar in the compound material I is Ar₁、Ar₂Identical or different in occurrence, and preferably one of the following structures:

4. the carbazole unit-containing organic semiconductor material according to claim 1, 2 or 3, characterized in that the compound material I may be embodied as the following molecular material structure:

5. a process for the preparation of an organic semiconductor material containing carbazole units as claimed in claim 1, characterized in that

Preparing 1, 8-dibromocarbazole and key intermediates of derivatives, and preparing a compound material I through a coupling reaction; wherein, the preparation of the 1, 8-dibromocarbazole and the derivatives takes N-ethyl-3, 6-di-tert-butyl-1, 8-dibromocarbazole as an example, and the specific steps are as follows:

wherein, the step I comprises an alkylation reaction under the condition of KOH/DMSO/ethyl bromide; step II is to add tBuCl/ZnCl₂/CH₂NO₃Carrying out tert-butylation under the conditions of (1); step III is carried out at AcOH/Br₂Carrying out a bromination reaction under the conditions of (1); and fourthly, carrying out boronization reaction under the action of nBuLi/organic boric acid ester.

6. The method for preparing an organic semiconductor material containing carbazole units according to claim 5, wherein in the method for synthesizing the compound I material, the coupling reaction is Suzuki method, Stille method, Yamamoto method; wherein,

method 1) Suzuki coupling reaction with aryl diboronic acid and/or aryl dihalide and 2 equivalents of aryl monohalide and/or aryl monoboronic acid, or mixed aromatic halide/boric acid, with palladium catalyst to effect coupling; the amount of the catalyst is 0.1 to 20 mol%; suitable solvents are weakly polar or polar aprotic organic solvents or mixtures thereof; the reaction is carried out at a temperature of 30 to 150 ℃; the reaction time is 1 to 7 days;

method 2) Stille coupling reaction: where the reactants are dihalide and/or distannate and monostannate and/or monohalide, or corresponding monohalide-monostannate derivative monomers, coupled under basic conditions and in the presence of a palladium catalyst and a solvent;

method 3) Yamamoto coupling reaction: the reactant is a halide; the reaction is carried out under alkaline conditions, Ni (0) or Ni (II) or compound catalysis and solvent conditions; the reaction conditions are Ni (1, 5-cyclooctadiene)₂Bipyridine/1, 5-cyclooctadiene/DMF.

7. The method for applying the carbazole unit-containing organic semiconductor material according to claim 1, wherein when the compound material I is used as a material of a light-emitting diode device, the structure of the light-emitting diode device is a transparent anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, or a cathode, wherein the carbazole unit-containing organic semiconductor material is used as the hole transport layer or the light-emitting layer, or as a host material of the light-emitting layer.